CN110828308B - Method for manufacturing semiconductor device and etching gas - Google Patents

Method for manufacturing semiconductor device and etching gas Download PDF

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Publication number
CN110828308B
CN110828308B CN201811552535.4A CN201811552535A CN110828308B CN 110828308 B CN110828308 B CN 110828308B CN 201811552535 A CN201811552535 A CN 201811552535A CN 110828308 B CN110828308 B CN 110828308B
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molecule
group
film
semiconductor device
gas
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CN110828308A (en
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堀内三成
佐佐木俊行
长谷川智
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Kioxia Corp
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Kioxia Corp
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
    • H01L21/3105—After-treatment
    • H01L21/311—Etching the insulating layers by chemical or physical means
    • H01L21/31105—Etching inorganic layers
    • H01L21/31111—Etching inorganic layers by chemical means
    • H01L21/31116—Etching inorganic layers by chemical means by dry-etching
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
    • H01L21/306—Chemical or electrical treatment, e.g. electrolytic etching
    • H01L21/3065—Plasma etching; Reactive-ion etching
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
    • H01L21/3105—After-treatment
    • H01L21/311—Etching the insulating layers by chemical or physical means
    • H01L21/31144—Etching the insulating layers by chemical or physical means using masks
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
    • H01L21/3205—Deposition of non-insulating-, e.g. conductive- or resistive-, layers on insulating layers; After-treatment of these layers
    • H01L21/321—After treatment
    • H01L21/3213—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer
    • H01L21/32133—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer by chemical means only
    • H01L21/32135—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer by chemical means only by vapour etching only
    • H01L21/32136—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer by chemical means only by vapour etching only using plasmas
    • H01L21/32137—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer by chemical means only by vapour etching only using plasmas of silicon-containing layers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
    • H01L21/3105—After-treatment
    • H01L21/311—Etching the insulating layers by chemical or physical means
    • H01L21/31127—Etching organic layers
    • H01L21/31133—Etching organic layers by chemical means
    • H01L21/31138—Etching organic layers by chemical means by dry-etching

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Abstract

Embodiments provide a method of manufacturing a semiconductor device and an etching gas that can etch a film by a preferable fluorocarbon-containing gas. The method for manufacturing a semiconductor device according to the embodiment etches a film using an etching gas containing a 1 st or 2 nd molecule, the 1 st or 2 nd molecule having C 3 F 4 The group (C represents carbon, F represents fluorine), and the number of carbon atoms is 4 or 5. Further, the 1 st molecule has a double bond to the C 3 F 4 An R1 group of carbon atoms within the group, the R1 group comprising carbon and comprising chlorine, bromine, iodine, or oxygen. Further, the 2 nd molecule is bonded to the C through a single bond 3 F 4 R2 groups of carbon atoms in the radical, bonded to the C by single bonds 3 F 4 An R3 group of carbon atoms within the group, at least one of the R2 group and the R3 group comprising carbon, and each of the R2 group and the R3 group comprising hydrogen, fluorine, chlorine, bromine, iodine, or oxygen.

Description

Method for manufacturing semiconductor device and etching gas
[ related application ]
The present application enjoys priority of japanese patent application No. 2018-150773 (filing date: day 2018, month 9). The present application includes the entire contents of the basic application by reference to the basic application.
Technical Field
Embodiments of the present application relate to a method for manufacturing a semiconductor device and an etching gas.
Background
When using C 4 F 6 When forming a recess in a film to be processed by etching with a fluorocarbon gas containing carbon and fluorine, such as a gas, a fluorocarbon film is deposited on the side surface of the film to be processed in the recess, and the side surface of the film to be processed during etching is protected by the fluorocarbon film. C (C) 4 F 6 The gas has the advantages of high deposition rate of the fluorocarbon film, but also has the disadvantages of high unit price, and the like. Thus, it is required to be C 4 F 6 Preferred fluorocarbon-containing gases are gases that replace the gases.
Disclosure of Invention
Embodiments provide a method of manufacturing a semiconductor device and an etching gas that can etch a film by a preferable fluorocarbon-containing gas.
The method for manufacturing a semiconductor device according to the embodiment etches a film using an etching gas containing a 1 st or 2 nd molecule, the 1 st or 2 nd molecule having C 3 F 4 The radical (C represents a carbon atom,f represents fluorine), and the number of carbon atoms is 4 or 5. Further, the 1 st molecule has a double bond to the C 3 F 4 An R1 group of carbon atoms within the group, the R1 group comprising carbon and comprising chlorine, bromine, iodine, or oxygen. Further, the 2 nd molecule is bonded to the C through a single bond 3 F 4 R2 groups of carbon atoms in the radical, bonded to the C by single bonds 3 F 4 An R3 group of carbon atoms within the group, at least one of the R2 group and the R3 group comprising carbon, and each of the R2 group and the R3 group comprising hydrogen, fluorine, chlorine, bromine, iodine, or oxygen.
Drawings
Fig. 1 (a) to (c) are cross-sectional views showing a method for manufacturing a semiconductor device according to embodiment 1.
FIG. 2 is a schematic diagram of a pair C 4 F 6 Graph of gas specification.
FIG. 3 is a schematic diagram of a pair C 4 F 6 Table for gas description.
FIG. 4 is a schematic diagram of a pair C 4 F 6 Another graph illustrating gas.
Fig. 5 (a) and (b) are diagrams for explaining the composition of the etching gas according to embodiment 1.
Fig. 6 to 9 are diagrams for explaining examples of the composition of the etching gas according to embodiment 1.
Fig. 10 is a cross-sectional view showing the structure of the semiconductor device of embodiment 1.
Detailed Description
Hereinafter, embodiments of the present application will be described with reference to the drawings. In fig. 1 to 10, the same or similar components are denoted by the same reference numerals, and overlapping description thereof is omitted.
(embodiment 1)
Fig. 1 is a cross-sectional view showing a method for manufacturing a semiconductor device according to embodiment 1. The semiconductor device of this embodiment mode is a three-dimensional memory.
First, a lower layer 2 is formed on a substrate 1, and a laminated film including a plurality of sacrificial layers 3 and a plurality of insulating layers 4 alternately is formed on the lower layer 2 ((a) of fig. 1). The sacrificial layer 3 is an example of the 1 st film, and the insulating layer 4 is an example of the 2 nd film. Next, an upper layer 5 is formed on the laminated film, and a mask layer 6 is formed on the upper layer 5 ((a) of fig. 1).
The substrate 1 is, for example, a semiconductor substrate such as a silicon (Si) substrate. Fig. 1 (a) shows an X direction and a Y direction parallel to and perpendicular to the surface of the substrate 1, and a Z direction perpendicular to the surface of the substrate 1. In the present specification, the +z direction is regarded as the upward direction, and the-Z direction is regarded as the downward direction. The Z direction may or may not coincide with the direction of gravity.
The lower layer 2 is, for example, a silicon oxide film (SiO 2 ) Or an insulating film such as a silicon nitride film (SiN) or a conductive layer formed between the insulating films. The sacrificial layer 3 is, for example, a silicon nitride film, and the insulating layer 4 is, for example, a silicon oxide film. The upper layer 5 is an insulating film such as a silicon oxide film or a silicon nitride film, or a conductive layer formed between insulating films. The mask layer 6 is, for example, a hard mask layer such as an organic film, a metal film, or a silicon-containing film. Examples of the silicon-containing film are a silicon oxide film, a silicon nitride film, a polysilicon film, and the like.
Next, an opening pattern for forming the memory hole M is formed on the mask layer 6 by photolithography and dry etching (fig. 1 (b)). Next, a memory hole M is formed through the upper layer 5, the plurality of insulating layers 4, the plurality of sacrificial layers 3, and the lower layer 2 by dry etching using the mask layer 6 (fig. 1 (b)). The aspect ratio of the memory hole M is, for example, 10 or more. The memory hole M is an example of a recess.
The memory hole M of the present embodiment is formed by dry etching using an etching gas containing a fluorocarbon-containing gas. As a result, in the dry etching, the protective film 7 is deposited on the side surfaces of the insulating layer 4 and the sacrificial layer 3 in the memory hole M, and the side surfaces of the insulating layer 4 and the sacrificial layer 3 are protected by the protective film 7. The protective film 7 of the present embodiment is C m F n Film (fluorocarbon film). Wherein C represents carbon, F represents fluorine, m and n represent integers of 1 or more.
The etching gas of the present embodiment contains the 1 st molecule or the 2 nd molecule as the molecule containing fluorocarbon gas. The 1 st molecule and the 2 nd molecule have C 3 F 4 Base (CF-cf=cf 2 Base), symbol "-" represents a single bond, symbol "=" tableShowing double bonds. The number of carbon atoms in the 1 st molecule is 4 or 5. Similarly, the number of carbon atoms in the 2 nd molecule is 4 or 5.
The 1 st molecule is further bonded to C through double bond 3 F 4 R1 is a carbon atom in the radical. The R1 group contains carbon, and contains chlorine (Cl), bromine (Br), iodine (I), or oxygen (O). R1 radicals are, for example, CCl 2 A radical or a CO radical. The R1 radical further comprises hydrogen (H) or fluorine (F).
Molecule 2 further comprises a bond to C via a single bond 3 F 4 R2 groups of carbon atoms in the radical, bound to C by single bonds 3 F 4 R3 groups of carbon atoms in the radicals. At least one of the R2 groups and the R3 groups comprises carbon, and each of the R2 groups and the R3 groups comprises hydrogen, fluorine, chlorine, bromine, iodine, or oxygen. The combination of R2 and R3 groups being, for example, CH 3 And a radical and F radical.
C 3 F 4 The radicals are also included in C 4 F 6 Functional groups in the molecule. As a result, it was found from the present embodiment that dry etching was performed by using such an etching gas, and that C was used 4 F 6 The same gas conditions can increase the deposition rate of the protective film 7. Thus, the memory hole M can be formed while the side surfaces of the insulating layer 4 and the sacrificial layer 3 in the memory hole M are preferably protected by the protective film 7. Details of the effects of the present embodiment will be described below.
Next, the protective film 7 and the mask layer 6 are removed, and the block insulating film 11, the charge storage layer 12, and the tunnel insulating film 13 are sequentially formed in the memory hole M ((c) of fig. 1). Next, the blocking insulating film 11, the charge storage layer 12, and the tunnel insulating film 13 are removed from the bottom of the memory hole M, and the channel semiconductor layer 14 and the core insulating film 15 are sequentially formed in the memory hole M ((c) of fig. 1). The charge storage layer 12 is, for example, a silicon nitride film. The channel semiconductor layer 14 is, for example, a polysilicon layer. The barrier insulating film 11, the tunnel insulating film 13, and the core insulating film 15 are, for example, silicon oxide films or metal insulating films.
Thereafter, the sacrificial layer 3 is removed to form a plurality of voids between the insulating layers 4, and a plurality of electrode layers are formed in the voids. Further, various plugs, wirings, interlayer insulating films, and the like are formed on the substrate 1. Thus, the semiconductor device of the present embodiment is manufactured.
In the following, for C 4 F 6 The details of the gas will be described, and the details of the etching gas of the present embodiment will be described based on the content thereof.
FIG. 2 is a schematic diagram of a pair C 4 F 6 Graph of gas specification.
When etching the insulating layer 4 and the sacrificial layer 3 using the mask layer 6 such as an organic film, a metal film, or a silicon-containing film, C is used 4 F 6 When (hexafluoro-1, 3-butadiene) gas is used as the etching gas, a higher mask selection ratio can be obtained. As a reason for obtaining such a higher selection ratio, C 4 F 6 The gas generates a large amount of protective film 7.
FIG. 2 shows the use of C 4 F 6 Deposition rate of protective film 7 in the case of gas and use of C 4 F 8 Deposition rate of the protective film 7 in the case of gas. When C is used 4 F 6 When the gas is used as the etching gas, the deposition rate of the protective film 7 becomes high, and thus a large amount of the protective film 7 is generated.
FIG. 3 is a schematic diagram of a pair C 4 F 6 Table for gas description.
In use C 4 F 6 In the case of gas as etching gas, the etching gas from C 4 F 6 The molecular plasma etches the insulating layer 4 and the sacrificial layer 3. Specifically, the protective film 7 is deposited by radicals contained in the plasma and contributing to deposition, and the insulating layer 4 and the side surface of the sacrificial layer 3 are etched by radicals and ions contained in the plasma and contributing to etching.
FIG. 3 shows the process from C 4 F 6 28 radicals produced by the molecule. What kind of radicals among these contribute to the deposition of the protective film 7 is described with reference to fig. 4.
FIG. 4 is a schematic diagram of a pair C 4 F 6 Another graph illustrating gas.
FIG. 4 shows C when the addition amount of the rare gas to the etching gas is changed 3 F 4 Free ofRadical density of radicals and deposition rate of the protective film 7. C (C) 3 F 4 The radical density of (2) is normalized based on the density in the case where the addition amount of the rare gas is zero.
Here, C 4 F 6 The molecule has CF 2 ＝CF-CF＝CF 2 Is a structure of (a). Due to CF 2 The double bond with CF is weaker and is therefore believed to be readily accessible from C 4 F 6 Molecular production of C 3 F 4 Free radicals and CF 2 And (3) free radicals. Thus, survey C 3 F 4 The relationship between the radical density of the radicals and the deposition rate of the protective film 7 is found from the above-mentioned relationship, and the relationship is C 3 F 4 There is a correlation between the radical density of the radicals and the deposition rate of the protective film 7 (fig. 4). Based on the result, it is considered that C 3 F 4 The radicals contribute to the deposition of the protective film 7.
Fig. 5 is a diagram for explaining the composition of the etching gas according to embodiment 1. The etching gas of the present embodiment contains the 1 st or 2 nd molecule as the molecule containing fluorine gas.
Fig. 5 (a) shows the structural formula of the 1 st molecule. Molecule 1 has C 3 F 4 Radicals, bound to C by double bonds 3 F 4 R1 is a carbon atom in the radical. The total number of carbon atoms in the 1 st molecule is 4 or 5. The R1 group comprises carbon and comprises chlorine, bromine, iodine, or oxygen. The R1 radical further comprises hydrogen or fluorine.
FIG. 5 (b) shows the structural formula of the 2 nd molecule. Molecule 2 has C 3 F 4 A group bonded to C by a single bond 3 F 4 R2 groups of carbon atoms in the radical, bound to C by single bonds 3 F 4 R3 groups of carbon atoms in the radicals. The total number of carbon atoms in the 2 nd molecule is 4 or 5. At least one of the R2 groups and the R3 groups comprises carbon, and each of the R2 groups and the R3 groups comprises hydrogen, fluorine, chlorine, bromine, iodine, or oxygen.
In the step (b) of fig. 1, the insulating layer 4 and the sacrificial layer 3 of the present embodiment are etched using plasma generated from the 1 st or 2 nd molecule. Specifically, the protective film 7 is deposited by radicals contained in the plasma and contributing to deposition by the plasmaThe radicals and ions contained in the sub-body and contributing to the etching etch the sides of the insulating layer 4 and the sacrificial layer 3. The electron density of the plasma at this time is, for example, 5.0X10 9 ～2.0×10 11 Individual/cm 3 。
The 1 st molecule and the 2 nd molecule have C 3 F 4 A base. Thus, when plasma is generated from the 1 st or 2 nd molecule, the plasma is generated from the C 4 F 6 The same applies to the case of molecular generation of plasma, which can generate plasma containing C 3 F 4 Plasma of free radicals. According to the present embodiment, by C generated from the 1 st or 2 nd molecule 3 F 4 The radicals make the deposition speed of the protective film 7 faster, and a higher mask selection ratio can be achieved. In other words, according to the present embodiment, the molecule 1 or 2 can be used as C 4 F 6 Preferred fluorocarbon-containing gases are gases that replace the gases.
The etching gas according to this embodiment may be a mixed gas containing the 1 st or 2 nd molecule and other molecules, or may be a mixed gas containing two or more 1 st molecules, two or more 2 nd molecules, or both 1 st and 2 nd molecules. For example, the etching gas of the present embodiment may contain oxygen molecules, rare gas molecules (monoatomic molecules), or C in addition to the 1 st or 2 nd molecules a F b (fluorocarbon) molecules. Wherein a and b represent integers of 1 or more.
The total number of carbon atoms in the 1 st molecule of this embodiment is set to 4 or 5 as described above. The reason for this is that when the total number of carbon atoms in the 1 st molecule is 6 or more, the division C is generated from the 1 st molecule 3 F 4 The influence of radicals other than the radicals is increased, and there is a possibility that etching characteristics may be degraded. For the same reason, the total number of carbon atoms in the 2 nd molecule of this embodiment is set to 4 or 5.
The F/C ratio of fluorine atoms to carbon atoms in the R1 group or the F/C ratio of fluorine atoms to carbon atoms in the R2 and R3 groups is preferably set to 2 or less. The F/C ratio of the R1 group is a value obtained by dividing the number of F atoms in the R1 group by the number of C atoms in the R1 group. For example, when the number of C atoms in the R1 group is 2, the number of F atoms in the R1 group is preferably set to 4 or less (0 may be used). Similarly, the F/C ratio of the R2 and R3 groups is a value obtained by dividing the total number of F atoms in the R2 group and F atoms in the R3 group by the total number of C atoms in the R2 group and C atoms in the R3 group. The reason for this is that when these F/C ratios are greater than 2, the mask selection ratio becomes low.
Fig. 6 to 9 are diagrams for explaining examples of the composition of the etching gas according to embodiment 1.
FIG. 6 is a diagram illustrating the example of the 1 st molecule, showing the structural formulae of various molecules. The 1 st molecule of the present embodiment is obtained by replacing at least part of H atoms or F atoms of each molecule shown in fig. 6 with Cl atoms, br atoms, or I atoms. Wherein, in the case of replacing F atom with Cl atom, br atom or I atom, C is removed 3 F 4 F atoms contained in groups other than the radical are the subject of substitution.
Fig. 7 to 9 are diagrams for explaining the example of the 2 nd molecule, and show structural formulas of various molecules. Fig. 7 to 9 show various examples of the molecule 2 according to this embodiment. Further, the 2 nd molecule of the present embodiment can be obtained by replacing at least a part of the H atom or F atom of each molecule shown in fig. 7 to 9 with Cl atom, br atom, or I atom. Wherein, in the case of replacing F atom with Cl atom, br atom or I atom, C is removed 3 F 4 F atoms contained in groups other than the radical are the subject of substitution.
The 1 st molecule or the 2 nd molecule of the present embodiment is not limited to these molecules, and may have other compositions or structures.
Fig. 10 is a cross-sectional view showing the structure of the semiconductor device of embodiment 1.
Fig. 10 shows an example of a semiconductor device manufactured by the method of the present embodiment. Fig. 10 shows a memory cell portion and a step contact portion of the three-dimensional memory. In fig. 10, the lower layer 2 is constituted by the 1 st insulating film 2a, the source side conductive layer 2b, and the 2 nd insulating film 2c, and the upper layer 5 is constituted by the cover insulating film 5a, the drain side conductive layer 5b, the 1 st interlayer insulating film 5c, and the 2 nd interlayer insulating film 5 d. The channel semiconductor layer 14 is electrically connected to the diffusion layer L in the substrate 1. The sacrificial layer 3 is replaced with an electrode layer 3' comprising a tungsten (W) layer or the like. Electrode layer 3' is an example of film 1.
Fig. 10 further shows the contact plugs 16 formed in the contact holes H of the upper layer 5. Each contact plug 16 is formed so as to be electrically connected to the corresponding electrode layer 3'.
As described above, the memory hole M of the present embodiment is formed by using a memory having a structure C 3 F 4 The etching gas of the 1 st or 2 nd molecule of the radicals is formed. Thus, according to the present embodiment, the insulating layer 4 and the sacrificial layer 3 can be etched by a preferable fluorocarbon-containing gas. For example, C having a higher unit price is not used 4 F 6 Gas, and C 4 F 6 The gas also performs a preferred etch. According to the present embodiment, the memory hole M having a relatively high aspect ratio of, for example, 10 or more may also be formed in a preferred shape.
In addition, in the step (a) of fig. 1, instead of alternately forming the plurality of sacrificial layers 3 and the plurality of insulating layers 4 on the lower layer 2, a plurality of electrode layers 3' and a plurality of insulating layers 4 may be alternately formed on the lower layer 2. In this case, the step of replacing the sacrificial layer 3 with the electrode layer 3' is not required.
The dry etching according to the present embodiment is also applicable to steps other than the processing of the memory hole M, for example, to steps for processing a recess other than the memory hole M.
Although several embodiments have been described above, these embodiments are presented by way of example only and are not intended to limit the scope of the application. The novel methods and gases described in this specification can be implemented in a variety of other ways. The method and the gas form described in the present specification may be omitted, replaced, or modified in various ways within a range not departing from the gist of the application. The accompanying claims and the equivalents thereof are intended to cover such forms or modifications as would be included in the scope or gist of the application.

Claims (10)

1. A method of manufacturing a semiconductor device includes etching a film using an etching gas including a gas having C 3 F 4 A 1 st or 2 nd molecule having a group (C represents carbon, F represents fluorine) and 4 or 5 carbon atoms,
the 1 st molecule is represented by the following formula (1), wherein the R1 group contains carbon and contains chlorine, bromine, iodine, or oxygen,
the 2 nd molecule is represented by the following formula (2), wherein each of the R2 group and the R3 group contains hydrogen, fluorine, chlorine, bromine, iodine, or oxygen,
2. the method for manufacturing a semiconductor device according to claim 1, wherein an F/C ratio of fluorine atoms to carbon atoms in the R1 group or an F/C ratio of fluorine atoms to carbon atoms in the R2 and R3 groups is 2 or less.
3. The method for manufacturing a semiconductor device according to claim 1, wherein the etching gas further comprises oxygen molecules, rare gas molecules, and C a F b At least any one of the molecules, wherein a and b represent an integer of 1 or more.
4. The method for manufacturing a semiconductor device according to claim 1, wherein the film is etched by plasma generated from the 1 st or 2 nd molecule.
5. The method for manufacturing a semiconductor device according to claim 4, wherein the plasma contains C generated from the 1 st or 2 nd molecule 3 F 4 And (3) free radicals.
6. The method for manufacturing a semiconductor device according to claim 4 or 5, wherein electrons of the plasmaDensity of 5.0X10 9 ～2.0×10 11 Individual/cm 3 。
7. The method for manufacturing a semiconductor device according to claim 1, wherein the film comprises a plurality of 1 st films and a plurality of 2 nd films alternately formed on a substrate.
8. The method for manufacturing a semiconductor device according to claim 1, wherein in the etching, a recess having an aspect ratio of 10 or more is formed in the film.
9. An etching gas comprising a gas having C 3 F 4 A 1 st or 2 nd molecule having a group (C represents carbon, F represents fluorine) and 4 or 5 carbon atoms,
the 1 st molecule is represented by the following formula (1), wherein the R1 group contains carbon and contains chlorine, bromine, iodine or oxygen,
the 2 nd molecule is represented by the following formula (2), wherein each of the R2 group and the R3 group contains hydrogen, fluorine, chlorine, bromine, iodine or oxygen,
10. the etching gas of claim 9, further comprising oxygen molecules, rare gas molecules, and C a F b At least any one of the molecules, wherein a and b represent an integer of 1 or more.
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